Migration control resin compositions and methods of using the same on porous materials

ABSTRACT

Stable, aqueous, colloidal synthetic resin compositions comprising (1) from about 0.1 percent by weight to about 60 percent by weight of a colloidal synthetic resin; and (2) from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin, of a metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin, said metal being selected from the group consisting of zinc, copper, cobalt, nickel and chromium; and methods of applying the synthetic resin compositions to porous, absorbent materials and controlling the migration or spreading thereon or penetration thereinto by applying the synthetic resin compositions to the porous, absorbent materials and substantially immediately diluting the synthetic resin composition to substantially immediately coagulate and precipitate the synthetic resin composition.

United States Patent 1 1 Drelich et al.

MIGRATION CONTROL RESIN COMPOSITIONS AND METHODS OF USING THE SAME ON POROUS MATERIALS Inventors: Arthur H. Drelich, Plainfield;

George J. Lukacs, Perth Amboy, both of NJ.

Johnson & Johnson, New Brunswick, NJ.

Filed; Mar. 8, 1974 Appl. N0.: 449,309

Assignee:

[56] References Cited UNITED STATES PATENTS 2,455,937 12/1948 Lowe 260/29.6 2,901,452 8/1959 West 260/29.6 3,026,281 3/1962 Harren... 260/29.6 3,629,179 12/1971 Bristol... 260/29.6 3,706,595 12/1972 Drelich 117/38 1 Dec. 30, 1975 3,821,146 6/1974 Drelich 260/29.6

FOREIGN PATENTS OR APPLICATIONS 568,554 1/1959 Canada 260/29.6

Primary Examiner-Donald E. Czaja Assistant Examiner-Edward Woodberry [57] ABSTRACT Stable, aqueous, colloidal synthetic resin compositions comprising (1) from about 0.1 percent by weight to about 60 percent by weight of a colloidal synthetic resin; and (2) from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin, of a metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxycontaining thickening resin, said metal being selected from the group consisting of zinc, copper, cobalt, nickel and chromium; and methods of applying the synthetic resin compositions to porous, absorbent materials and controlling the migration or spreading thereon or penetration thereinto by applying the synthetic resin compositions to the porous, absorbent materials and substantially immediately diluting the synthetic resin composition to substantially immediately coagulate and precipitate the synthetic resin composition.

8 Claims, No Drawings MIGRATION CONTROL RESIN COMPOSITIONS AND METHODS OF USING THE SAME ON POROUS MATERIALS The present invention relates to improved stable, aqueous, colloidal synthetic resin compositions and to methods of utilizing the same. More specifically, the present invention relates to stable, aqueous, colloidal synthetic resin compositions which are intended to be applied to porous or absorbent materials such as textile materials, paper, paper products, wood leather, polyurethane, vinyl and other foams, wall board, concrete, cinder block, etc. and to methods of applying such colloidal synthetic resin compositions to such porous or absorbent materials on which or into which the extent of the migration, diffusion, penetration, or spreading of such colloidal synthetic resin compositions is controlled. Y

GENERAL BACKGROUND In many industries such as the textile, paper, paper products, wood, leather, polyurethane foam, printing arts, decorative arts, building materials and like industries, there is often a need to apply a stable, aqueous synthetic resin composition to porous or absorbent materials and to maintain such synthetic resin composition in the same shape, size and configuration, as well as in the same location, on the porous or absorbent materials where it was originally applied without undesirably migrating, penetrating, or spreading materially therefrom in any direction to any substantial extent on or into the porous or absorbent materials.

Such resins have found use in the coating industries for the coating of woven, knitted, nonwovenand other textile fabrics, paper, paperproducts, wood, leather and other related materials. The resins are also used as adhesives for laminating materials or for bonding fibrous webs. These resins have also found wide use as additives in the manufacture of paper, the printing industry, the decorative printing of textiles, and in other industries.

PURPOSES AND OBJECTS It is therefore a principal purpose and object of the present invention to provide improved, stable, aqueous, colloidal synthetic resin compositions which can be applied to porous or absorbent materials in such fashion as to control the extent of the migration, diffusion, penetration or spreading of the resin composition on or into the porous or absorbent materials.

STATEMENT OF THE INVENTION It has been found that such purpose and object, as well as other purposes and other objects which will become clear from a further reading hereof, may be achieved by applying to the porous or absorbent materials a stable, aqueous, colloidal, synthetic resin composition comprising from about 0.1 to about 60 percent by, weight, and preferably from about 5 to about 50 percent by weight, on a solids basis, of a colloidal synthetic resin, and from about 0.01 percent by weight to about 2 percent by weight, and preferably from about 0.05 percent by weight to about 1 percent by weight, based on the weight of the colloidal synthetic resin, (solids/solids basis) of a water-soluble metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening-resin, said metal being selected from the group-consisting of zinc, copper, cobalt, nickel and chromium and controlling the migration or spreading thereon or penetration thereinto by substantially immediately diluting the synthetic resin composition to substantially immediately coagulate and precipitate the synthetic resin composition.

1 PREFERRED ILLUSTRATIVE EMBODIMENT The present invention will be described in greater particularity herein purely for illustrative but not limitative purposes insofar as it relates to porous, absorbent fibrous sheet materials and to their methods of manufacture. More particularly, however, the present invention is concerned with the so-called bonded, nonwoven textile fabrics, i.e., fabrics produced from textile fibers without the use of conventional spinning, weaving, knitting or felting operations.

Although not limited thereto, the invention is of primary importance in connection with nonwoven fabrics derived from oriented or carded fibrous webs composed of textile-length fibers, the major proportion of which are oriented predominantly in one direction.

Another aspect of the present invention is its application to nonwoven fabrics wherein the textile-length fibers were originally predominantly oriented in one direction but have been reorganized and rearranged in predetermined designs and patterns of fabric openings and fiber bundles.

Still another aspect of the present invention is its application to nonwoven fabrics wherein the textilelength fibers are disposed at random by air-laying techniques and are not predominantly oriented in any one direction. Typical nonwoven fabrics made by such procedures are termed isotropic nonwoven fabrics.

And still another aspect of the present invention is its application to nonwoven fabrics which comprise wood pulp fibers and/or textile-length fibers and which are made basically by conventional or modified aqueous paper making techniques. Such fabrics are also basically isotropic and generally have like properties in all directions.

The conventional base starting material for the majority of these nonwoven fabrics is usually a fibrous web comprising any of the common textile-length fibers, or mixtures thereof, the fibers varying in average length from approximately one-half inch to about two and one-half inches. Exemplary of such fibers are the natural fibers such as cotton and wool and the synthetic or man-made cellulosic fibers, notably rayon or regenerated cellulose.

Other textile length fibers of a synthetic or man-made origin may be used in various proportions to replace either partially or perhaps even entirely the previouslynamed fibers. Such other fibers include: polyamide fibers such as nylon 6, nylon 66, nylon 610, etc.; polyester fibers such as Dacron, Fortrel and Kodel; acrylic fibers such as Acrilan, Orlon and Creslan; modacrylic fibers such as Verel and Dynel; polyolefinic fibers derived from polyethylene and polypropylene; cellulose ester fibers such as Arnel and Acele; polyvinyl alcohol fibers; etc.

These textile-length fibers may be replaced either partially or entirely by fibers having an average length of less than about one-half inch and down to about one-quarter inch. These fibers, or mixtures thereof, are customarily processed through any suitable textile machinery (e.g., a conventional cotton card, a Rando- 3 Webber, a paper making machine, or other fibrous web producing apparatus) to form a web or sheet of loosely associated fibers, weighing from about 100 grains to about 2000 grains per square yard or even higher.

If desired, even shorter fibers, such as wood pulp fibers or cotton linters, may be used in varying propor tions, even up to 100 percent, where such shorter length fibers can be handled and processed by available apparatus. Such shorter fibers have lengths less than one-quarter inch.

The resulting fibrous web or sheet, regardless of its method of production, is then subjected to at least one of several types of bonding operations to anchor the individual fibers together to form a self-sustaining web. One method is to impregnate the fibrous web over its entire surface area with various well-known bonding agents, such as natural or synthetic resins. Such overall impregnation produces a nonwoven fabric of good longitudinal and cross strength, acceptable durability and washability, and satisfactory abrasion resistance. However,-the nonwoven fabric tends to be somewhat stiff and boardlike, possessing more of the properties and characteristics of paper or board than those of woven or knitted textile fabric. Consequently, although suchoverall impregnated nonwoven fabrics are satisfactory for many uses, they are still basically unsatisfactory as general purpose textile fabrics.

Another well-known bonding method is to print the fibrous webs with intermittent or continuous straight or wavy lines, or areas of binder extending generally transversely or diagonally across the web and additionally, if desired, along the fibrous web. The resulting nonwoven fabric is far more satisfactory as a textile fabric than overall impregnated webs in that the softness, drape and hand of the resulting nonwoven fabric more nearly approach those of a woven or knitted textile fabric.

The printing of the resin binder on these nonwoven webs is usually in the form of relatively narrow lines, or elongated rectangular, triangular or square areas, or annular, circular, or elliptical binder areas which are spaced apart a predetermined distance which, at its maximum, is preferably slightly less than the average fiber length of the fibers constituting the web. This is based on the theory that the individual fibers of the fibrous web should be bound together in as few places as possible.

These resin colloidal dispersions, or resin emulsions, or latexes, may be anionic, non-ionic or even polyionic, and stable dispersions are available commercially at pHs of from about 2 /2 to about 10. For the purposes of the present invention, however, those resin compositions having low, acidic pH s must be pretreated, such as with sufficient ammonia, to bring them into the pH range of from about 7 up to about 10. It is in this pH range that the resin compositions of the present invention are used.

The amount of resin which is applied to the porous or absorbent material varies within relatively wide limits, depending upon the resin itself, the nature and character of the porous or absorbent materials to which the resins are being applied, its intended use, etc. A general range of from about 4 percent by weight up to about 50 percent by weight, based on the weight of the porous or absorbent material, is satisfactory under substantially all uses. Within the more commercial limits, however, a range of from about 10 to about percent by weight,

based on the weight of the porous or absorbent materials is preferred.

The nominal surface coverage of such binder lines or areas will vary widely depending upon the precise properties and characteristics of softness, drape, hand and strength which are desired in the final bonded product. ln'practice, the nominal surface coverage can be designed so that it falls within the range of from about 10 to about 50 percent of the total surface of the final product. Within the morecommercial aspects of the present invention, however, nominal surface coverages of from about 12m about 40 percent are preferable.

In certain cases, especially where larger proportions of short fibers are used, surface coverages of up to about percent are often encountered and such are preferred in some applications of the present invention.

Such bonding increases the strength of the nonwoven fabric and retains substantially complete freedom of movement for the individual fibers whereby the desirable softness, drape and hand are obtained. This spacing of the binder lines and areas has been accepted by the industry and it has been deemed necessarily so, if the stiff and board-like appearance, drape and hand of the overall impregnated nonwoven fabrics are to be avoided.

The nonwoven fabrics bonded with such line and area binder patterns have had the desired softness, drape and hand and have not been undesirably stiff or board-like. However, such nonwoven fabrics have also possessed some disadvantages.

For example, the relatively narrow binder lines and relatively small binder areas of the applicator (usually an engraved print roll) which are laid down on the fibrous web possess specified physical dimensions and interspatial relationships as they are initially laid down. Unfortunately, after the binder is laid down on the wet fibrous web and before it hardens or becomes fixed in position, it tends to spread, diffuse or migrate whereby its physical dimensions are increased and its interspatial relationships decreased. And, at the same time, the binder concentration in the binder area is lowered and rendered less uniform by the migration of the binder into adjacent fibrous areas. One of the results of such migration is to make the surface coverage of the binder areas increase whereby the effect of the intermittent bonding approaches the effect of the overall bonding. As a result, some of the desired softness, drape and hand are lost and some of the undesired properties of harshness, stiffness and boardiness are increased.

It is therefore desirable that the narrow binder lines remain narrow and that they do not migrate into wide binder lines. As pointed out previously, such desirable features are provided by the use of the resin compositions of the present invention.

As pointed out previously, the resin composition which is applied to the porous or absorbent materials comprises (1) a colloidal synthetic resin and (2) a water-soluble metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin as a migration control agent.

The Colloidal Synthetic Resins The colloidal synthetic resins may be selected from a relatively large group of synthetic resins well known in industry for bonding, coating, impregnating or related uses, and may be of a self cross-linking type, externally cross-linking type, or not cross-linked. Specific examples of such synthetic resins include: polymers and copolymers of vinyl ethers; vinyl halides such as plasticized and unplasticized polyvinyl chloride, polyvinyl chloride-polyvinyl acetate, ethylene-vinyl chloride, etc.; polymers and copolymers of vinyl esters such as plasticized and unplasticized polyvinyl acetate, ethylene-vinyl acetate, acrylic-vinyl acetate; etc.; polymers and copolymers of the polyacrylic resins such as ethyl acrylate, methyl acrylate, butyl acrylate, ethylbutyl acrylate, ethyl hexyl acrylate, hydroxyethyl acrylate, dimethyl amino ethyl acrylate, etc; polymers and copolymers of the polymethacrylic resins such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, etc.; polymers and copolymers of acrylonitrile, methacrylonitrile, acrylamide, N-isopropyl acrylamide, N-methylol acrylamide, methacrylamide, etc.; vinylidene polymers and copolymers, such as polyvinylidene chloride, polyvinylidene chloridevinyl chloride, polyvinylidene chloride-ethyl acrylate, polyvinylidene chloride-vinyl chloride-acrylonitrile, etc; polymers and copolymers of polyolefinic resins including polyethylene, polypropylene, ethylene-vinyl chloride and ethylene-vinyl acetate which have been listed previously; the synthetic rubbers such as 1,2- butadiene, 1,3-butadiene, 2-ethyl-l,3-butadiene, high, medium and carboxylated butadiene-acrylonitrile, butadiene-styrene, chlorinated rubber, etc., natural latex; the polyurethanes; the polyamides, the polyesters; the polymers and copolymers of the styrenes including: styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-ethyl styrene, 4-butyl styrene; phenolic emulsions; etc.

These resins may be used either as homopolymers comprising a single repeating monomer unit, or they may be used as copolymers comprising two, three, or more different monomer units which are arranged in random fashion, or in a definite order alternating fashion, within the polymer chain. Also included within the inventive concept are the block polymers comprising relatively long blocks of different monomer units in a polymer chain and graft polymers comprising chains of one monomer attached to the backbone 'of another polymer chain.

The Migration Control Agent To the aqueous dispersion of colloidal synthetic resin solids is added a small amount of from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin of a water-soluble metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin.

The water-soluble metal ammine coordination complex of the high molecular weight, water-soluble polymeric, polycarboxy-containing thickening resin is formed by reaction of l) a suitable metal salt and (2) ammonium hydroxide and (3) a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin.-

The Metal Salt The metal salt is water-soluble and the metal or cation portion is selected from the group consisting of zinc, copper, cobalt, nickel and chromium. Specific examples of such water-soluble salts are zinc acetate, zinc bromide, zinc butyrate, zinc chlorate, zinc chloride, zinc formate, zinc iodide, zinc lactate, zinc nitrate, zinc sulfate, etc.; copper (ll) acetate, copper (II) metaborate, copper (ll) bromate, copper chlorate, copper (ll) chloride, copper (II) fluoride, copper (ll) formate, copper (ll) lactate, copper (ll) nitrate, copper (ll) sulfate, etc.; cobalt (II) acetate, cobalt (ll) benzoate, cobalt (II) bromate, cobalt (Il) chloride, cobalt (ll) iodide, cobalt (II) chlorate, cobalt (Il) nitrate, cobalt (lll) chloride, cobalt (ll) sulfate, cobalt (Il) iodide, etc.; nickel acetate, nickel chloride, nickel nitrate, nickel sulfate, etc; chromium (II) and (Ill) acetate, chromium (ll) bromide, chromium (Ill) nitrate, chromium (ll) chloride, chromium (II) and (Ill) oxalate, chromium sulfate, etc. Many of these salts are preferably used in the form of their hydrates which possess greater solubility in water.

The Ammonium Hydroxide The ammonium hydroxide may be used in any form or in any concentration but is preferably used in the standard, commercially available concentration (aqueous, 28% NH;,). Unless specifically stipulated otherwise, this commercially available form is the form used herein. 7

The Water-Soluble, High Molecular Weight, Polymeric Polycarboxy-Containing Thickening Resin The high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin may be selected from a relatively large group of such polycarboxylic materials which include, for example: polyacrylic acid; polymeric crotonic acid; copolymers of vinyl acetate and acrylic acid; polyacrylic acid-polyacrylarnide copolymers; polymethacrylic acid; polymethacrylic acid-polyacrylamide copolymers; carboxymethyl cellulose; carboxyethyl cellulose; carboxypropyl cellulose; polycarboxymethyl hydroxyethyl cellulose; alginic acid; polymers of acrylic acid and acrylic acid esters; polymers of 04,,8- unsaturated carboxylic acids such as itaconic acid; etc. These water-soluble, polymeric, carboxylic thickeners may be used in their acid forms but normally it is preferred to use their water-soluble neutralized salts, that is, their sodium, potassium, lithium, ammonium, or like water-soluble salts.

It is to be observed that all of these high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resins contain generally a main long chain comprising a large number of monomeric units from which the carboxylic groups extend. It is not essential that only carboxylic groups extend from the main long chain; other groups may so extend such as in the case of acrylic acid-acrylamide copolymers. In the case of monomeric units having more than one site for a carboxylic radical, such as in the case of carboxymethyl cellulose which may contain up to three sites, it is not essential that all sites have the carboxylic radical. There merely must be a sufficie'nt number of carboxylic groups to react with the metallic salt to pave the way for subsequent coagulation and precipitation.

It is believed that the chemical structure of the migration control agent is as follows; with the long horizontal line generally representing the main long chain of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin from which the carboxylic radicals or groups originally extended:

In this structural formula, only two carboxylate groups are shown but it is to be appreciated that there are many more carboxylate groups. It is also to be appreciated that it is not essential that all the carboxylic groups of the polycarboxylic polymer be reacted with the metal salt and that only from about 20 to about 100 percent need be so reacted for the purposes of the present invention. Also, in the structural formula, Me represents the metal cation of the metal salt; X represents the average number of ammonia groups attached via coordinate complex bonds to the metal (Me) and has a numerical range of from a very low fractional value less than one up to a maximum value of four; and A represents the anion derived from the metal salt used and may be acetate, metaborate, bromate, bromide, butyrate, chlorate, chloride, fluoride, formate, iodide, lactate, nitrate, sulfate, and the like.

Another way to set forth this structural formula is therefore as follows:

wherein m n 100 percent; m 20 to 100 percent; and n to 80 percent; and the other symbols are as previously described.

The colloidal synthetic resin composition containing the colloidal synthetic resin and the water-soluble metal ammine coordination complex of the high molecular weight, water-soluble, polymeric, polycarboxycontaining thickening resin is applied to the porous or absorbent material and is substantially immediately diluted whereby it is substantially immediately coagulated and precipitated in place under controlled migration conditions. a

The dilution may be effected in different ways in order to activate the reaction mechanism. For example, the porous or absorbent fibrous material may be pretreated by being pre-wet with a sufficient quantity of an aqueous medium, preferably water, whereby the colloidal resin composition immediately becomes sufficiently diluted. Or, if desired, the colloidal resin composition may be first printed on the porous or absorbent fibrous material and then substantially immediately treated with the aqueous medium such as water to effect the dilution whereupon the colloidal resin particles substantially immediately agglomerate or coagulate in place with no further spreading, diffusion or migration.

The amount of the water applied to the fibrous web varies widely, depending upon many factors, the most important of which is the nature, concentration, properties and characteristics of the synthetic resin, the metal ammine complex coordination compound, and the surfactant system in which they are stabilized. Normally, the amount of water applied to the fibrous web is in the range of from about 140 to about 280 percent,

and preferably from about 160 to about 220 percent, based on the dry weight of the fibrous web being treated. Such amounts are controlled by the use of suitable conventional vacuum apparatus, nip rolls, squeeze-rolls, etc.

The amount of water which is applied to the fibrous web prior to the printing of the resin binder also affects the degree of control exercised over the coagulation and migration. The greater the amount of water, the greater is the control and the more rapid is the coagulation and the less the migration. On the other hand, the less the amount of water in the fibrous web, the less is the control exercised, the less rapid is the coagulation, and the greater is the migration.

The degree of coagulation may be lowered even more and the degree of migration may be increased by the inclusion in the pre-wetting water of a small amount of an alkaline or basic material such as ammonium hydroxide. The pH remains alkaline, just as it does in other variations of this invention, and the coagulation and precipitation are purely the result of the dilution.

When printed on a pre-wetted fibrous web during the manufacture of nonwoven fabrics, the total migration of the resin binder solids may be reduced to as little as about 50 percent or less beyond the originally deposited area. In some instances, themigration is relatively negligible. Normally, however, the increase in area of the resin binder solids, even under the most adverse conditions, does not materially exceed about 200 percent. Such values are to be compared to increases in binder migration of at least about 300 percent and up to about 800 percent when emulsion polymerized resins are applied to fibrous porous absorbent sheet materials, unaided by the principles disclosed herein.

The concentration of the binder resin solids in the binder area is correspondingly increased when utilizing the principles of the present invention and is in the range of from about 50 percent by weight to about 120 percent by weight, and more normally from about 60 to about percent by weight, based on the weight of the fibers in the binder area.

The invention will be further illustrated in greater detail by the following specific examples. It should be understood, however, that although these examples may describe in particular detail some of the more specific features of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not to be construed as limited thereto.

EXAMPLE I A water-soluble metal ammine coordination complex of a water-soluble, high molecular weight, polymeric, polycarboxy-containing thickening resin is prepared as follows:

50 ml. of a 1% zinc acetate aqueous solution is added to 1 pound of a 2% aqueous solution of COLLATEX ARM EXTRA, a low viscosity ammonium alginate (2000 cps, Brookfield LVF, 30 rpm, No. 3 spindle). The viscosity rises to 2300 cps. An additional 45 ml. of the 1% zinc acetate aqueous solution is added to the ammonium alginate aqueous solution. The viscosity rises to 2500 cps. 5 ml. of ammonium hydroxide (aqueous, commercial, 28% NH is added. The viscosity drops to 1000 cps. The pH is 9.5. The zinc ammine alginate coordination complex is thus formed.

Five additional 50 ml. quantities of the 1% zinc acetate aqueous solution are added successively. The pH drops successively to 9.1, 8.9, 7.9, 7.7 and 7.7 with each addition. The viscosity rises at the same time respectively to 1200 cps, 1700 cps, 2300 cps, 4100 cps, and 6400 cps. The zinc ammine alginate coordination complex aqueous solutions are of use in controlling resin migration in subsequent Examples.

Viscosities, as set forth herein and in all Examples, are measured in centipoises, as determined on a Brookfield Viscosimeter, Model LVF, 30 rpm, using a No. 3 spindle.

EXAMPLE II The procedures of Example I are followed substantially as set forth therein except that the zinc acetate is replaced by an equivalent (stoichiometric) amount of zinc chloride, zinc nitrate, zinc sulfate, copper nitrate, copper chloride, copper sulfate, cobalt-nitrate, cobalt chloride, nickel sulfate, nickel chloride, chromium sulfate, and chromium chloride. The copper cobalt and chromium are divalent. Chromium (Ill) sulfate is also used in the form of its hydrates.

The'resultsof each substitution are generally comparable to those obtained in Example 1 and the resulting metal ammine alginate complexes are of use in controlling resin migration in the subsequent Examples.

EXAMPLE III A fibrous card web weighing about 530 grains per square yard and comprising 100 percent bleached rayon fibers, 1 /2' denier and 19/16 inches in length is intermittently print bonded by the rotogravure process using an engraved roll having 4% horizontal wavy lines per inch. The width of each line, as measured on the engraved roll is 0.024 inch.

The composition by weight of the resin binder composition used for the intermittent print bonding is:

6 pounds of NS4260, primarily a self cross-linking polyethyl acrylate acrylic polymer (50 percent solids latex).

1 pound of the zinc ammine alginate complexaqueous solution prepared in Example 1 l000cps). 40 ml. of a 50:50 water: ammonia (aqueous, commercial, 28% NH to a pH of 7.5 and a viscosity of 680.

The fibrous card web is pretreated or pre-moistened with alarge amount of water to the extent of about 190 percent moisture based on the dry weight of the fibers in the card web. I

The extra moistening of the card web with water is sufficient by itself to upset the stability of the colloidal synthetic resin dispersion when it is subsequently applied to the fibrous card web and it substantially immediately coagulates and precipitateson the very wet fibrous card web under controlled migration, spreading, or penetration conditions. The printed web is then further processed, dried andcured, using conventional or standard nonwoven fabric. manufacturing techniques.

EXAMPLE IV The procedures set forth in Example 111 are followed substantially as set forth therein with the exception that the NS4260 self cross-linking polyethyl acrylate acrylic polymer (50 percent solids latex) is replaced by an equivalent weight of other polymers, namely:

. Vinacryl 4322" a vinyl acetate-acrylic copolymer (50% solids latex) B. EVA 1968 an ethylene-vinyl acetate copolymer (50% solids latex) C. NS2892 a polyvinyl acetate polymer (51.5% solids latex) D. GEON 576" a polyvinyl chloride-lower alkyl acrylate copolymer (46% solids latex) E. CAP 243" a butadiene-styrene copolymer (50% solids latex) an ethylene-vinyl acetate copolymer (55% solids latex) F. Airflex 510 Goodrich an ethyl acrylate-acrylonitrile 2671" copolymer (46% solids latex) NS Resyn a polyvinyl acetate-acrylate 2345" copolymer (55% solids latex) a polyethyl acrylate polymer 1: R&H HA-8" (50% solids latex) The results are generally comparable to those obtained in Example 111. The binder migration control is excellent in controlling resin migration during the bonding of the bonded nonwoven fabric.

EXAMPLE V The procedures set forth in Example III are followed substantially as set forth therein with the exception that the zinc ammine alginate complex is replaced by other metal ammine complexes of other high molecular weight, water-soluble polymeric, polycarboxy-containing thickening resins, namely;

A. The zinc ammine complex of l. Acrysol 51" an acrylic acid-acrylamide copolymer (molecular weight 375,000- 500,000)

(D.S. 0.65-0.85) (molecular weight in excess of 200,000) (D.S. 0.65-0.85) (molecular weight in excess of 70,000) (D.S. 1.2-1.4) (molecular weight in excess of 100,000)

2. Hercules Carboxymethyl Cellulose 7H35 3. Hercules Carboxymethyl Cellulose 7M 4. Hercules Carboxymethyl Cellulose I2M8 Polyacrylic Acid Goodyear Carboset 514" polyacrylate copolymer 7. R&H Acrysol A-S polyacrylate homopolymer These zinc ammine complexes are prepared generally by the procedures set forth in Example 1, replacing the alginate by other high molecular weight, water-soluble, polymeric, polycarboxy-containing thickeningresins such as a acrylic acid-acrylamide copolymer, carboxymethyl cellulose, polyacrylic acid, polyacrylate copolymers and homopolymers, etc.

The results are generally comparable to those obtained in Example Ill. The resin migration control is excellent in bonding of the bonded nonwoven fabric.

EXAMPLE Vl EXAMPLE Vll An additional binder migration control agent is prepared, using the following preparation:

300 ml. water 300 ml. SUPERLOID 1% ammonium alginate ml. comm. ammonia 3 grams zinc acetate 10 ml. water Viscosity is 120 cps. pH is 10.4

0.50 pounds of this preparation is formulated with 5 pounds of NS4260 and ml. comm. ammonia to pH 8.6. Viscosity is 760 cps. Binder migration control is good when the formulation is applied in a nonwoven fabric bonding operation.

EXAMPLE VIll An additional binder migration control is prepared using the following preparation:

300ml. water 300 ml. SUPERLOlD 1% ammonium alginate 15 ml. comm. ammonia 15 grams zinc acetate 45 ml. water Viscosity is 60 cps. pH is 9.8

0.5 pounds of this preparation is formulated with 5 pounds of NS4260 and 100 ml. comm. ammonia. Viscosity is 600 cps. Resin migration control is good,

EXAMPLE lX The procedures of Example I are followed substantially as set forth therein with the exception that the ammonium alginate is replaced by Kelgin F which is a sodium salt of alginic acid. The results are generally comparable to those obtained in Example I and the resulting metal ammine alginate complexes are of use in controlling resin migration as described herein.

Although the present invention has been described and illustrated with reference to preferred embodiments thereof, it is to be appreciated that such is merely for the purpose of disclosing the invention and is not to be construed as limitative of the broader aspects of the inventive concept, except as defined by the appended claims.

It is also to be appreciated that these preferred embodiments, particularly as noted in the illustrative working examples, enumerate primarily only the essential or critical constituents in the various formulations and that other constituents such as anti-oxidants, anticorrosion agents, pigments, foam inhibitors, surfactants, and other additives, have not been set forth specifically.

What is claimed is:

1. Stable, aqueous, colloidal synthetic resin compositions comprising: I) from about 0.1 percent by weight to about 60 percent by weight of a colloidal synthetic resin; and (2) from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin, of a metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin selected from the group consisting of naturally occurring carboxylic acids, carboxy-containing cellulosics and the salts of said carboxylic acids and cellulosics, said metal being selected from the group consisting of zinc, copper, cobalt, nickel and chromium.

12 2. A synthetic resin composition as defined in claim 1 wherein the metal ammine coordination complex of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin has the structural formula:

wherein the long horizontal line represents the main long chain of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin from which carboxylic groups extend; Me is a metal from the group consisting of zinc, copper, cobalt, nickel and chromium; X is a small fractional number less than one up to four; A is an anion; and the ratio of m/(m+n) is from about 0.20 to l.

3. A synthetic resin composition as defined in claim 1 wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is alginic acid.

4. A synthetic resin composition as defined in claim 1 wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is car boxymethyl cellulose.

5. A method of applying a stable, aqueous, colloidal synthetic resin compositions to porous materials and controlling its migration thereon which comprises applying to porous materials a stable, aqueous, colloidal synthetic resin composition comprising: 1) from about 0.1 percent by weight to about 60 percent by weight of the colloidal synthetic resin; and (2) from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin of a metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin selected from the group consisting of naturally occurring carboxylic acids, carboxy-containing cellulosics and the salts of said acids and said cellulosics, said metal being selected from the group consisting of zinc, copper, cobalt, nickel and chromium; and substantially immediately diluting the synthetic resin composition to substantially immediately coagulate and precipitate the synthetic resin composition.

6. A method of applying a synthetic resin composition to porous materials and controlling its migration thereon as defined in claim 5, wherein the metal ammine coordination complex of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin has the structural formula:

14 thereon as defined in claim 5, wherein the high molecular weight, water-soluble polymeric, polycarboxy-containing thickening resin is alginic acid.

8. A method of applying a synthetic resin composition to porous materials and controlling its migration thereon as defined in claim 5, wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is carboxymethyl cellulose. 

1. STABLE, AQUEOUS, COLLOIDALY SYNTHETIC RESIN COMPOSITIONS COMPRISING: (1) FROM ABOUT 0.1 PERCENT BY WEIGHT TO ABOUT 60 PERCENT BY WEIGHT OF A COLLOIDAL SYNTHETIC RESIN; AND (2) FROM ABOUT 0.01 PERCENT BY WEIGHT TO ABOUT 2 PERCENT BY WEIGHT, BASED ON THE DRY SOLIDS WEIGHT OF THE COLLOIDAL SYNTHETIC RESIN, OF A METAL AMMINE COORDINATION COMPLEX OF A HIGH MOLECULAR WEIGHT, WATER-SOLUBLE, POLYMERIC, POLYCARBOXY-CONTAINING THICKENING RESIN SELECTED FROM THE GROUP CONSISTING OF NATURALLY OCCURING CARBOXYLIC ACIDS, CARBOXY-CONTAINING CELLULOSICS AND THE SALTS OF SAID CARBOXYLIC ACIDS AND CELLULOSICS, SAID METAL BEING SELECTED FROM THE GROUP CONSISTING OF ZINC, COPPER, COBALT, NICKEL AND CHROMIUM.
 2. A synthetic resin composition as defined in claim 1 wherein the metal ammine coordination complex of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin has the structural formula:
 3. A synthetic resin composition as defined in claim 1 wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is alginic acid.
 4. A synthetic resin composition as defined in claim 1 wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is carboxymethyl cellulose.
 5. A method of applying a stable, aqueous, colloidal synthetic resin compositions to porous materials and controlling its migration thereon which comprises applying to porous materials a stable, aqueous, colloidal synthetic resin composition comprising: (1) from about 0.1 percent by weight to about 60 percent by weight of the colloidal synthetic resin; and (2) from about 0.01 percent by weight to about 2 percent by weight, based on the dry solids weight of the colloidal synthetic resin of a metal ammine coordination complex of a high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin selected from the group consisting of naturally occurring carboxylic acids, carboxy-containing cellulosics and the salts of said acids and said cellulosics, said metal being selected from the group consisting of zinc, copper, cobalt, nickel and chromium; and substantially immediately diluting the synthetic resin composition to substantially immediately coagulate and precipitate the synthetic resin composition.
 6. A method of applying a synthetic resin composition to porous materials and controlling its migration thereon as defined in claim 5, wherein the metal ammine coordination complex of the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin has the structural formula:
 7. A method of applying a synthetic resin composition to porous materials and controlling its migration thereon as defined in claim 5, wherein the high molecular weight, water-soluble polymeric, polycarboxy-containing thickening resin is alginic acid.
 8. A method of applying a synthetic resin composition to porous materials and controlling its migration thereon as defined in claim 5, wherein the high molecular weight, water-soluble, polymeric, polycarboxy-containing thickening resin is carboxymethyl cellulose. 